Diazo-type multicolor reproduction process

ABSTRACT

A COLORING MATERIAL IN USE FOR THE DIAZO-TYPE MULTICOLOR REPRODUCTION WHICH COMPRISES A THERMOVOLATILE OR THERMOSUBLIMATIVE ACID ADDITION SALT OF A THERMOVOLATILE OR THERMOSUBLIMATIVE AZO COUPLING COMPONENT HAVING AN AMINO GROUP, AND A DIAZO-TYPE MULTICOLOR REPRODUCTION PROCESS USING SUCH COLORING MATERIAL.

United States Patent M 3,725,066 DIAZO-TYPE MULTICOLOR REPRODUCTIONPROCESS Kouzi Nihyakumen, Toshihiro Kouchi, and Taizo Yokoyama, Osaka,Yasuo Ueda, Kobe, and Yasutoki Kamezawa and Tatsuo Aizawa, Osaka, Japan,assignors to Mita Industrial Company Limited, Osaka, Japan No Drawing.Filed Aug. 31, 1970, Ser. No. 68,518 Claims priority, application Japan,Sept. 1, 1969, 44/68,938 Int. Cl. G03c 5/34, 1/58 US. Cl. 9649 8 ClaimsABSTRACT OF THE DISCLOSURE A coloring material in use for the diazo-typemulticolor reproduction which comprises a thermovolatile orthermosublimative acid addition salt of a thermovolatile orthemosublimative azo coupling component having an amino group, and adiazo-type multicolor reproduction process using such coloring material.

This invention relates to a coloring material useful in diazo-typemulticolor reproduction. More detailedly, the invention relates to acoloring material useful in diazotype multicolor reproduction comprisinga thermovolatile substance which can color portions of a photosensitivepaper corresponding to predetermined portions of an original selectivelyto different hues without substantial mingling of colors.

We previously proposed a process for diazo-type multicolor reproductionbased on the discovery that predetermined portions of an original can bereproduced into different hues regardless of difference or similarity ofthe light transmission in the original by conducting the steps of (A)exposing to light a diazo-type photosensitive material containing atleast one diazonium salt (c) and (B) heating a layer of at least onethermovolatile or thermosublimative coupler disposed in a face-to-facecontact with the diazo-type photosensitive material at a portioncorresponding to a predetermined portion of an original, the steps beingcarried out coincidentally or in an order of (A) to (B) or (B) to (A),and then developing the exposed photosensitive material in the pressureof a coupler (b) having a lower coupling rate under developing conditions than the thermovolatile or thermosublimative coupler (a).

In this diazo-type multicolor reproduction process a thermovolatile orthermosublimative coupler is applied to the back surface of one or morepredetermined portions of a transparent or semi-transparent original.

This heat-transferable coupler is applied in the form of an ink-likecomposition, waxy composition or the like to the back surface of anoriginal by coating, transferring or other procedures, but in general,thermovolatile or thermosublimative couplers are chemically instable andtend to be easily discolored. When the coupler applied to the backsurface of an original is discolored and the light transmission lowered,coloration is caused to occur in portions other than the portionscorresponding to the predetermined portions of the original by thedevelopment treatment, with the result that a copied image excellent indistinctness cannot be obtained.

In the above-mentioned diazo-type multicolor reproduction process, thethermovolatile or thermosublimative coupler is heat-transferred from thecoupler layer applied to the back surface to a diazo-type photosensitivematerial. It has been experientially found that under some reproducingconditions only several multicolored copies can be obtained from onetreated original.

It has now been found that the above defects can be overcome by using athermovolatile or thermosublimative 3,725,066 Patented Apr. 3, 1973 acidaddition salt of a thermovolatile or thermosublimative acid additionsalt of a thermovolatile or themosublimative azo coupling componentcontaining an amino group.

Accordingly, a primary object of this invention is to provide a coloringmaterial in use for the diazo-type multicolor reproduction process whichis chemically stable by itself and accordingly is excellent in storagestability.

Another object of this invention is to provide a coloring material inuse for the diazo-type multicolor reproduction process, which does notsubstantailly damage the transparency or semi-transparency of theoriginal when it is applied to the back surface of the original bycoating, writing, transferring or bonding, and which can color onlyportions corresponding to the predetermined portions of the original andgive multicolored copies having an image accurately corresponding to theimage of the original.

Still another object of this invention is to provide a coloring materialfor use in diazo-type multicolor reproduction process which makes itpossible to produce stably a great many multicolored copies from oneoriginal treated with a heat-transferable coupler.

The above-mentioned objects of this invention can be attained by acoloring material useful in diazo-type multicolor reproduction whichcomprises a thermovolatile or thermosublimative acid addition salt of athermovolatile or thermosublimative azo coupling component containing anamino group.

Suitable thermovolatile or thermosublimative azo coupling componentscontaining an amino group may be selected from aminopheuols, aromaticamines and amines containing active methylene groups. Typical examplesof such azo couplers are as follows:

Aminophenols and benzene type amines:

Meta-aminophenol Para-aminophenol Ortho-aminophenolMeta-phenylenediamine Para-phenylenediamine 2-amino-paracresolS-amino-orthocresol 3-amino-paracresol S-amino-orthocresolPara-chloroaniline Meta-aminobenzoic acid 3,4-diamino-paratoluene Activemethylene groupcontaining amino compounds:

1-phenyl-3-methyl-pyrazolone( 5 1-phenyl-3-carboxypyrazolone3-methylpyrazolone Acetoacetic acid anilide Acetoacetic-o-chloroanilidePara-carboxyacetoacetoanilide Any of the above-mentioned couplers may beused in this invention but it is preferable to use those having amelting point of -150 C. Among them particularly preferred are thosewhose thermovolatility or thermosublimativity is highly increased whenconverted to an acid addition salt. As typical instances of suchcoupling component there may be cited meta-aminophenol andphenylmethylpyrazolone.

M.P. C.) Meta-aminophenol 122 Meta-aminophenol hydrochloride L19l-phenyl-3-methylpyrazolone(5) 127 1-phenyl-3-methylpyrazolone(5)hydrochloride 96 When the coloration tests were effected with use of theabove-mentioned coupling components in combination with a diazo-typephotosensitive material comprising 3 4-diazo-N,N-dimethylanilinechloride /zZnCl double salt and2,7-dihydroxynaphthalene-3,6-disulfonicacid sodium salt, it was foundthat while free-meta-aminophenol can give -20 copies, its hydrochloridecan give 30-40 copies under the same conditions, and that use of thehydrochloride salt of 1-phenyl-3-methylpyrazolone(5) can increase thenumber of copies by -30 sheets as compared with freel-phenyl-3-methylpy1'azolone(5).

In this invention, the above-mentioned couplers are used in the form ofacid addition salts. Any acid is used for forming the acid additionsalts of the coupling components, as long as the resulting salts arethermovolatile or thermosublimative.

As acids preferably used in this invention there may be cited thefollowing compounds:

Inorganic acids such as hydrochloride, hydrobromic acid, and otherhydrohalogenic acids;

Organic sulfonic acids such as p-toluene sulfonic acid, and o-toluenesulfonic acid; and

Carboxylic acids such as chloroacetic acid (CICH -COOH), chloropropionicacid (ClCH CH -COOH), acetic acid (CH COOH),

salicylic acid (C H (OH) (COOH)), 2,6-dichlorobenzoic acid (C H C(COOH)), 3,4-dimethylbenzoic acid (C H (CH COOH), oxalic acid ((COOH)2),

oxalic acid hydrate ((COOH) -2H O), o-sulfobenzoic acid (C H (CO H)(SOH)+3H O), trichloroacetic acid (CCl COOH),

formic acid (HCOOH),

benzoic acid (C H COOH),

methacrylic acid (CH =C(CI-I )COOH), and butyric acid (CH CH CH COOH).

The preparation of acid addition salts of azo coupling components may beaccomplished according to a customary method by mixing an azo couplingcomponent with an acid such as cited above in a suitable medium.

In accordance with this invention, the acid addition salt of the azocoupling component is formed into a coating composition by dispersingthe salt into a liquid, semi-solid or solid dispersion medium. Thepreparation of such coating composition will be described below byreferring to some examples. The acid addition salt may be prepared inadvance of the preparation of the coating composition, or it may beformed at the time of preparing the coating composition. In the lattercase, it is possible to make an excess of the acid present in thecomposition.

(1) Ink-like composition:

Thermovolatile acid addition salt of Percent Heat-transferable coupler5.0-25.0 Binder 0-5.0 Coloring material 0-3.0 Dispersing assistant 0-5.0Dispersion medium Balance As the dispersion medium aliphatic alcoholssuch as dimethyl formamide, ethanol, n-propanol, isopropanol andisobutyl alcohol, aromatic solvents such as benzene, toluene andxylene,esters, OH-group-containing, neutral liquids having a boiling point of100-240 C., such as water, high boiling point alcohols, e.g., n-hexylalcohol, n-heptyl alcohol, 3-heptanol, 4-heptanol and octanol, andglycols, e.g., glycerin, ethylene glycol, propylene glycol, polyethylene glycol, 1,3-butadiol may be used, 1,4-butadiol and2,3-butadiol. These solvents may be used singly or in combination. Asthe thermovolatile acid addition salt those which a e mentioned ab e ybe dt is possible to incorporate a coloring material so as to confirmthe formation of a film of the composition, or to use a binder for thepurpose of obtaining a good fixation of the coupler.

The composition of the above recipe is applied to the back surface of aportion of the original predetermined to have a different hue by meansof a brush, an installed felt pen, a ball pen, a coating roller, asprayer or a printing machine.

(2) Waxy composition:

Thermovolatile acid addition salt of Percent Heat-transferable coupler5-25 Wax -15 Oil 10-40 Coloring material 0-200 The composition of theabove recipe is shaped to have a crayon stick-like form or a chalk-likeform, and the back surface of a portion of an original predetermined tohave a different hue is painted therewith. It is also possible to form apressure-sensitive transfer sheet by melting the above composition ordissolving it in a suitable solvent and coating the melt or solution ona substrate such as paper and plastic film. The so formedpressure-sensitive transfer sheet is overlapped on the back surface ofan original sheet, and then pressing is effected thereon by means of atypewriter or other writing means to form a heat-transferable layer onthe back surface of an image predetermined to have a different hue.

(3) Coupler-transferring sheet: The ink-like composition which isdescribed in (l) or a composition obtained by incorporating a binder oran extender into such inklike composition is coated on a transparent orsemitransparent sheet such as paper, plastic film or non-woven fabric.The so formed sheet for heat-transferring the coupler is cut into adesired size, if necessary, and then applied to the back surface of aportion of an original determined to have a different hue. It ispossible to form a pressure-sensitive adhesive layer on the back surfaceof the coupler-transferring layer for preventing it from exfoliatingfrom the original.

The original treated with the coloring material of this invention forthe diaZo-type multicolor reproduction is piled on a diazo-typephotosensitive material containing at least one diazonium salt (c) andthe assembly is subjected to the light exposure and the treatment forheat transferring the coloring material. The light-exposured andheat-transferred photosensitive material is then developed in thepresence of a coupler (b) having a lower coupling rate than the coloringmaterial under development conditions.

The multicolor reproduction with the use of the coloring material ofthis invention is performed by the following procedures.

At least one layer of the coloring material of this invention is appliedto the back surface of one or more predetermined portions of atransparent or semi-transparent original to form an original for themulticolor reproduction. The so formed original for the multicolorreproduction is overlapped on a diazo-type photosensitive materialcontaining at least one diazonium salt (c) in a manner such that thephotosensitive surface of the photosensitive material will confront theheat-transferable coupler layer, and the light-exposure and heating areeffected coincidentally or successively in this order or the reverseorder. Thus, the heat-transferable coupler (a) is heat-transferred tothe surface of the predetermined portion of the photosensitive material,and the light resolution of the diazonium salt (c) in the photosensitivematerial is caused to occur depending on the light transmission of theoriginal. When the so exposed photosensitive material is developed by amethod known per se, at the predetermined portion to which the coupler(a) of the coloring material has been heat-transferred, the diazoniumsalt (0) at the non-exposed area reacts Selectively and preferentiallywith the coupler to form a dyestuff (c)- (a) and at other portion thediazonium salt at the non-exposed area reacts with the coupler (b)having a lower coupling rate than the heat-transferable coupler (a) toform a dyestulf (c)-(b). Thu-s, there is obtained a multicoloredreproductive copy in which the predetermined portion is colored in a huedifferent from that of the other portion.

It is essential that among the thermovolatile or thermosublimative acidaddition salt coupler (a) of the coloring material, coupler (b) anddiazonium salt (c) to be used in this invention there should beestablished the follow ing relations:

(I) Therrnovolatile or thermosublimative coupler (a) has a highercoupling rate under developing conditions than coupler (b).

(II) Dyestulf (b)-(c), dyestuff (a)(c), dyestuff (a)-(c) formed at thedevelopment have hues different from one another.

As the coupling component (b) having a lower coupling rate than thecoupler component (a) of the coloring material of this invention phenolderivatives, naphthols, active methylene group-containing compounds,heterocyclic compounds and other couplers usually used in the diazo-typephotosensitive materials may be used. Specific examples of thesecouplers are as follows.

Phenol derivatives:

2,5,6-trimethylphenol 2-hydroxymethylphenol fl- (Z-hydroxyphenyl-propionic acid 2-(w-phenylaminomethyl)-phenol[8-(4-methyl-2-hydroxyphenyl)-glutaric acid 2, -dimethyl-6-N-dimethylaminomethyl) -phenol 1,3-dimethyl ether of pyrogallola-Resorcylic acid ethanolamine B-Resorcylic acid N-lauryl-p-aminophenolN-acyl-m-aminophenol Meta-hydroxy-acetoanilideOrtho-N-hydroxyphenyl-monoguanidine Para-N-hydroxyphenyl-biguanidine2,5-dimethyl-4-morpholinomethyl phenol2-methyl-5-isopropyl-morpholinomethyl phenol4-morpholinomethylresorcinol monomethyl ether 3,3',5-trihydroxydiphenyl3,3,5,5'-tetrahydroxydiphenyl 2,2',4,4-tetrahydroxydiphenyl2,4,4-trihydroxydiphenyl-2'-sulfonic acid2,4,6,3',5-pentahydroxydiphenyl 2,2,4,4-tetrahydroxydiphenyl sulfideNaphthols:

2,B-dihydroxynaphthalene-6-sulfonic acid 2-naphthol-3,6-disulfonic acid2,7-dihydroxynaphthalene-3-sulfonic acid2,8-dihydroxynaphthalene-fi-sulfonic acid1,B-dihydroxynaphthalene-8-sulfonic acid 1,S-aminonaphthol-5-sulfonicacid 2,7-dihydroxy-3,6-disulfonic acid1,8-benzoylaminonaphthol-Z-sulfonic acid1,8-dihydroxynaphthalene-6-sulfonic acidZ-hydroxy-3-naphthionic-N-B-hydroxyethyl amideZ-hydroxy-3-naphthionic-N,N-bis-fl-hydroxyl ether amide8-hydroxy-Z-naphthionic-hydroxyethyl amide1-(N-carboethoxymethylamino)-8-naphthol-4- sulfonic acidS-(para-nitro)-benzamido-1-naphthol l-hydroxynaphthyl-7-phenyl-guanidine2-hydroxynaphthyl-8-biguanidine1-naphthol-3-(N-p3-hydroxyethyl)-sulfonic amide 1-naphthol-3-(N-o-methoxyphenyl)-sulfonic amide Bis- [5-hydroxy-7-sulfo-naphthyl (2)]amine N,N-bis] l-hydroxy-S-sulfo-naphthyl(6) ]-thiourea As thediazonium salt-containing diazo-type photosensitive materialone-component photosensitive materials containing a diazonium salt andan optional assistant, and two-component photosensitive materialscontaining a diazonium salt, a coupler (b) and an optional assistant maybe used. Suitable photosensitive materials are chosen depending on thedeveloping method. These photosensitive materials are usually composedof a substrate such as paper, plastic film, fibrous textile, non-wovenfabric, and metal foil, and coated thereon, a sensitizing composition.The preparation of such photosensitive material will now be described byreferring to some examples.

(A) Sensitizing composition for dry development:

1 Percent Azo coupling component (b) (having a lower coupling rate thanheat-transferable coupling component (a) of the coloring material) 0.5-4Diazo compound (0) 0.2-4 Non-volatile organic acid 0.1-5.0 Coloringmatter 0-0.025 Development accelerator 1-10 Extender O-2.5 Solvent.Balance The sensitizing composition of the above recipe is coated on asubstrate such as paper and plastic film, and dried to form aphotosensitive sheet.

(B) Two-component type sensitizing composition for wet development:

Percent Azo coupling component (b) (having a lower coupling rate thanheat-transferable coupler component (a) of the coloring material) 0.5-4Diazo compound (c) 0.2-4 Organic acid (non-volatile) 0.1-5.0 Extender0-2.5 Coloring matter 0-0.025 Solvent Balance The sensitizingcomposition of the above recipe is coated on a substrate such as paperand plastic film, and

dried to form a photosensitive sheet.

Any of conventional photo-resoluble diazonium salts may be used in theabove-mentioned composition, as long as it is capable of coupling withthe heat-transferable coupling oomponent (a) of the coloring materialand the coupler (b) having a lower coupling rate than the couplingcomponent (a), under development conditions.

Examples of such diazonium compounds are as follows:

Para-phenylene-diamine-N,N-substituted compounds of the followinggeneral formula:

wherein X stands for an anion, R and R" each are aliphatic groups, and Zand Y denote groups which can be introduced into the benzene nucleus.

Specific examples of the compounds of this type are as follows:

4-diazo-N,N-dimethyl aniline (referred to simply as MA salt)4-diazo-N,N-diethyl aniline (referred to simply as EA salt)4-diazoN-ethyl-N-fl-hydroxyethyl aniline (referred to simply as EH salt)4-diazo-N,N-bis-fi-hydroxyethyl aniline4-diazo-N-methyl-N-B-hydroxyethyl aniline4-diazo-N-ethyl-N-fl-hydroxypropyl aniline Other diazonium salts ofp-phenylene diamines N,N- substituted with alkyl or hydroxy-alkyl groups4-diazo-N-ethyl-N-(,8-diethylamino)-ethyl aniline4-diazo-2-chloro-N,N-dicthyl aniline 4-diazo-2-methyl-N,N-diethylaniline 4diazo-2-iodo-N,N-diethyl aniline4-diazo-2-trifiuoromethyl-N,N-diethyl aniline 4-diazo-N-ethyl-N-benzylaniline 4-diazo-N-methyl-N-benzyl aniline (referred to simply as methylbenzyl) Aminohydroquinone ether-type compounds of the following generalformula:

wherein R, R and R" are alkyl or aryl groups and X stands for an anion.

Specific examples of the compounds of the above type are as follows:

4-diazo-2,5-dibutoxy-N,N-diethyl aniline 4-diazo-2,S-diethoxy-N-benzoylaniline (referred to simply as BB salt)4-diazo-2,S-diethoxy-N-ethyl-N-benzoyl aniline4-diazo-2,S-dibenzyloxy-N-benzoyl aniline4-diazo-2-chloro-S-methoxy-N-benzoyl aniline4-diazo-2,S-diethoxy-N-benzoyl-methyl aniline4-diazo-2,S-diethoxy-N-benzoyloxy-methyl aniline Other4-diazo-2,5-dioxyalkyl (or dioxyaryl)-'N-alkyl (or aryl) compounds andderivatives thereof Aminodiphenyl compounds, aminodiphenyl aminecompounds and their analogues of the following general formulas:

wherein X is an anion, R is a divalent aryl group, R-is a monovalent ordivalent aryl or alkyl group, A is a divalent group or a direct bond andexamples of the RAR' are diarylamine (A; NH-), diphenyl (A; directbond), diphenyl oxide (A; O-), diaryl methane (A; CH stilbene (A; CH=CH)and diaryl or dialkyl sulfide (A; -S).

Specific examples of the compounds of the above type are as follows:

Para-diazophcnyl amine 4-diazo-2,5,4-triethoxydiphenyl amine4-diazo-2,5,4'-triethoxydiphenyl 4,4'-bis-diazo-2,2',5 ,5-tetrahydroxydiphenyl methane Bis-diazo-8,8-dichloro-5,5-dimethoxybenzidine 4-diazo-2,S-dimethoxyphenylethyl sulfide4-diazo-2,5-diethoxy-4-methyl-diphenyl sulfide Heterocyclic aminederivatives'of the following general formula:

wherein X stands for an anion, Y and Z are groups which can beintroduced into the benzene nucleus, and A is a direct bond(phenylpyrrolidine) or a divalent group such as O- (morpholine), S-(thiomorpholine) and methylene (phenyl piperidine).

Specific examples of the compounds of this type are as follows:

4-diazo-2,5-dibutoxy-N-phenyl morpholine 4-diazo-2,5-diethoxy-N-phenylmorpholine 4-diazo-2-methoxy-N-thio morpholine 4-diazo-N-phenylpiperidine 4-diazo-N-phenyl pyrrolidine 4-diazo-2,5-di-n-butoxy-N-phenylpiperidine Other derivatives of 4-diazo-N-phenyl heterocyclic amines.

N,N-substituted ortho-phenylene diamine derivatives andorthoamino-phenol derivatives.

Specific examples of the compounds of this type are as follows:

2-diazo-4-methylmercapto-N,N'-dimethyl aniline2-diazo-5-benZoylamino-N,N'-dimethyl aniline2-diazo-1-naphthol-5-sulfonic acid The above-mentioned diazoniumcompounds may be used in the form of a relatively stable salt withsulfuric acid or hydrochloric acid. They may be also used in the form ofa double salt with zinc chloride, tin chloride, aluminum sulfate or thelike. Further, they may be used in the state stabilized by an arylsulfonate (in the form of a diazonium salt of an aromatic sulfonicacid), a diazosulfonate or the like. These diazonium salts may be usedeither singly or in the form of a mixture of two or more of them.

As the organic acid in the sensitizing composition citric acid, tartaricacid, oxalic acid, sulfamic acid, boric acid, phosphoric acid, etc. maybe used. As the extender there dextrin, gum arabic, colloidal silica,etc. may be used. As the stabilizers 1,3,6-naphthalene, sodiumtrisulfonate and'other aryl sulfonic acids may be used. Polyhydricalcohols such as glycerin and ethylene glycol are used as a developmentaccelerator. Coloring matters are used for indicating the photosensitiveface and increasing the whiteness of the background, and blue dyestuffssuch as Methylene Blue and Patent Blue are used for this purpose. As thesolvents water and organic solvent such as alcohols, acetone, toluene,xylene and esters may be used.

The so formed photosensitive sheet is piled on an original, on the backsurface of one or more predetermined portions of which theabove-mentioned coloring material has been applied in advance, in amanner such that the coloring material-treated back surface of theoriginal will confront the photosensitive layer of the photosensitivesheet. When the assembly is subjected to the light exposure and heating,the coupling component (a) of the coloring material is heat-transferredon the portions of the photosensitive sheet corresponding to thepredetermined portions of the original and the light resolution of thediazonium salt (0) is caused to occur depending on the lighttransmission of the original. The so treated photosensitive sheet isdeveloped in the presence of a coupler (b) having a lower coupling ratethan the coupling component (a) contained in the coloring material by amethod known per se. The coupler (b) having a relatively low couplingrate may be incorporated in the photosensitive material in advance ormay be contained in a developing liquid.

The developing may be conducted by either the dry method or the wetmethod. In the dry method, the development can be accomplished byexposing the heated and exposed photosensitive sheet to a mixed gas ofammonia and steam. In the case of a one-component type photosensitivepaper for the Wet development, a liquid developer having, for instance,the following recipe;

Percent Coupler (b) (having a lower coupling rate than theheat-transferable coupling component (a) of the coloring material)0.2-4.5

Alkaline agent 0.5-20 Reducing agent -20 Surfactant O-0.5

Water Balance is applied to the heated and exposed photosensitive sheetby a customary method such as dipping, roller coating, and spray coatingmethods. In the case of a two-component photosensitive sheet, thedevelopment is accomplished by contacting the heated and exposedphotosensitive sheet with an aqueous liquid developer containing analkaline agent.

In accordance with this invention, by employing the the'rmovolatile orthermosulblimative coupler (a) in the form acid addition salt, it ispossible to prevent effectively the coloring material used multicolorreproduction from being discolored during storage or after itsapplication to an original and to overcome the defect of theconventional product that the light transmission of the portion ofthe'original treated with the coloring material is lowered because ofthe contamination of the treated original. Thus, this invention canprovide distinct multicolored reproducti-ve copies in which portionscorresponding to predetermined portions of the original are coloredselectively in different hues.

Further, in accordance with this invention, it is possible to obtainfrom one treated original many copies, e.g., 30-400 distinct copies.

Examples of the preparation of ink-like compositions for treating theback surface of an original:

EXAMPLE 1 An ink-like composition of the following recipe is prepared asa yellow color-forming agent for treating the back surface of anoriginal:

Acetoacetic acid anilide acetate salt g 25 Ethylene glycol g 15 Alkydresin g 5 Ethanol ml 100 EXAMPLE 2 An ink-like composition of thefollowing recipe is prepared as a red color-forming agent for treatingthe back surface of an original:

1-phenyl-3-methylpyrazolone(5) .g 20 Hydrochloric acid (36%) ml Glycering 10 Ethanol ml 50 Water ml 50 The above composition is directly used asa material to be coated on the back surface of a portion of the originalto be reproduced in red by means of a brush, a coating roller or asprayer, or after it has been charged in a felt pen or a ball pen, it isused as a material for treating the back surface of a portion of theoriginal to be reproduced in red.

10 EXAMPLE 3 An ink-like composition of the following recipe is preparedas a brown color-forming agent for treating the back surface of anoriginal:

Meta-aminophenol hydrochloride g 30 Ethylene glycol g 15 Vinyl acetateresin g 5 Methanol ml 100 EXAMPLE 4 A yellowish brown color-formingagent is prepared by using meta-phenylene diamine hydrochloride insteadof meta-aminophenol hydrochloride in the composition of Example 3.

EXAMPLE 5 A yellow color-forming agent is prepared by using 3-amino-o-cresol hydrochloride instead of meta-aminophenol hydrochloridein the composition of Example 3.

Examples of the preparation of waxy agents for treating the back surfaceof an original:

EXAMPLE 6 A waxy composition to be used as a yellow color-forming agentfor treating the back surface of an original is prepared by heat meltingG. Metaphenylene diamine hydrochloride 30 Stearic acid 100 Paraffin '50Terra abla 50 Diatomaceous earth 20 and solidifying the melt.

The above composition is molded into a crayon sticklike form and is usedas a material to be coated on the back surface of a portion of theoriginal desired to be reproduced into a ditferent hue.

EXAMPLE 7 A waxy composition to be used as a brown colorforming agentfor treating the back surface of an original is prepared by heat meltingG. Meta-aminophenol hydrochloride 4O Parafl'in 50 Terra abla Haze wax 20Stearic acid 100 Magnesium carbonate 20 and solidifying the melt.

The so formed composition is molded into a crayon stick-like orchalk-like form and is used as a material for coating the back surfaceof a portion of an original desired to be reproduced in a different hue.

EXAMPLE 8 A waxy composition of the following recipe is prepared as ared color-forming agent for treating the back surface of an original:

G. 1-phenyl-3-methylparazolone(5) hydrochloride 20 Stearic acid ParaffinS0 Diatomaceous earth 30 Haze wax 20 The above composition is moldedinto a crayon sticklike or chalk-like form and is used as a material forcoating the back surface of a portion of the original desired to bereproduced in a different hue.

EXAMPLE 9 To the composition of Example 8 100 g. of mineral oil, 50 g.oleic acid and g. of Permanent Red are added, and the mixture is kneadedin a bowl mill to disperse additional components uniformly. Then, thekneaded mixture is coated on a substrate such as paper to obtain apressure-sensitive copy sheet. The so formed copy sheet is overlapped onthe back surface of an original and the pressing is effected thereon bymeans of a typewriter or other writing means. Thus, the sheet is used asa material for forming a layer of the waxy agent on the back surface ofan image of the original to be reproduced in a different hue.

Examples of the preparation of coupler-transferring sheets for treatingthe back surface of an original:

EXAMPLE 10 A composition of the following recipe is prepared as a browncolor-forming agent for treating the back surface of an original:

Meta-aminophenol hydrochloride g Triacetate resin g 10 Methanol mlAcetone ml 50 EXAMPLE 1 l A composition to be used as a redcolor-forming agent for treating the back surface of an original isprepared by using 1-phenyl-3-methylpyrazolone(5) hydrochloride insteadof meta-aminophenol hydrochloride in Example 10. From this composition asheet for heat-transferring the coupler cap-able of forming a red coloris formed.

APPLICATION EXAMPLE 1 Multicolor-forming diazo-type photosensitive paperin use for dry development A solution of the following recipe isprepared:

4 diazo N ethyl-N-hydroxyethylaniline chloride /2ZnCl 15 Diethyleneglycol Citric acid 20 2,3-dihydroxynaphthalene-6-sulfonic acid 7 Zincchloride 50' Thiourea 25 Patent Blue 0.1 Water Balance Total--1 liter.

The solution is coated on a base paper by a customary coating proceduresuch as using an air knife coater and dried to form a photosensitivesheet.

The sheet is overlapped on an original in which the back surface of aportion is treated with the ink-like composition prepared in Example 1and the back surface of another portion is treated with the ink-likecomposition prepared in Example 2. Then, the assembly is heated at -100C. and exposed to light by means of a mercury lamp to form a latentimage of the diazonium salt.

Next, the so treated sheet is subjected to development with gasifiedammonia and steam. Thus, a clear multicolor copy is obtained in which ata portion corresponding to the portion treated with the ink of Example 1the diazonium salt is colored in a yellow color, at a portioncorresponding to the portion treated with the ink of Example 2 thediazonium salt is colored in red and at an other portion correspondingto the untreated portion the diazonium salt is colored in bluish violet.The resulting copy is very clear and excellent in color distinction.

APPLICATION EXAMPLE 2 When Application Example 1 is repeated by usinginstead of 4-diazo-N-ethyl-N-hydroxyethyl-aniline chloride- /2ZnC1 4diazo N,N dimethylaniline chloride- /zZnCl a multicolor reproductivecopy similar to that of Application Example 1 is obtained.

APPLICATION EXAMPLE 3 Multicolor-forming photosensitive paper in use fordry development A solution of the following recipe is prepared:

G. 4-diazo-N,N-diethyl-aniline chloride' /2ZnCl l5 Ethylene glycol 50Citric acid 20 2,7-dihydroxynaphthalene-3,6-disulfonic acid sodium salt8 Zinc chloride 20 Thiourea l,3,6-naphthalene-trisulfonic acid sodiumsalt 20 Patent Blue 0.1

Water Balance Total-1 liter.

By a customary coating method such as using an air knife coater, aphotosensitive paper is prepared from the above solution. Thephoto-sensitive paper is overlapped on an original in which a portion ofthe back surface is treated with the ink-like composition prepared inExample 2 and another portion of the back surface is treated with thecomposition prepared in Example 3. The assembly is exposed to light andheated by means of a mercury lamp. Then, the so treated sheet issubjected to development with gasified ammonia and steam. Thus, a clearthree-color reproductive copy is obtained in which a portioncorresponding to the portion of the original treated with thecomposition of Example 2 is colored in red, a portion corresponding tothe portion treated with the composition of Example 3 is colored inbrown, and another portion corresponding to the untreated portion of theoriginal is colored in blue. The copy is very clear and excellent incolor distinction.

APPLICATION EXAMPLE 4 Multicolor-forming photosensitive paper for drydevelopment A solution of the following recipe is prepared:

Bis- [5-hydroxy-7-sulfonaphthyl (2 amine Zinc chloride 30 Thiourea 25Hydrochloric acid (36%) ml 10 Patent Blue g 0.1 Water Balance Totallliter.

By a customary coating method such as using an air knife coater, theabove solution is applied to a substrate of a photosensitive paper anddried. The so formed photosensitive paper is piled on an original, aportion of the back surface of which is treated with the waxycomposition prepared in Example 7 and another portion of the backsurface of which is treated with the waxy composition obtained inExample 8. Then the assembly is heated and printed by means of a mercurylamp, [followed by development with gaseous ammonia and steam. Thus aclear three-color reproductive copy in which a portion corresponding tothe portion treated with the treating agent of Example 7 is colored inbrown, another portion corresponding to the portion corresponding to theportion treated with the treating agent of Example 8 is colored in redand the remaining portion corresponding to the untreated portion iscolored in dark blue. The copy is very clear and excellent in colordistinction.

APPLICATION EXAMPLE Multicolor-forming photosensitive paper in use fordry development A solution of the following recipe is prepared:

G. 4-diazo-N,N-dimethylaniline chloride-VzZnCl 20 Diethylene glycol 50Tartaric acid 20 2,7-dihydroxynaphthalene-3,6-disulfonic acid sodiumsalt 8 Resorcinol monoethyl ether 3 Zinc chloride 1O Thiourea 501,3,6-naphthalene-trisulfonic acid sodium salt 20 Patent Blue 0.1 WaterBalance Total-1 liter.

In the same manner as in Example 1, a photosensitive paper is praperedfrom the above solution by coating and drying. The photosensitive paperis piled on an original, a portion of the back surface of which istreated with the coupler-heat-transferring sheet prepared in Example 10and another portion of the back surface of which is treated with thetreating agent obtained in Example 11. Then the assembly is heated andlight-exposed by means of a mercury lamp, followed by development withgaseous ammonia and steam. Thus there is obtained a clear threecolorreproductive copy is obtained in which a portion corresponding to theportion treated with the treating agent of Example 10 is colored inyellowish brown, another portion corresponding to the portioncorresponding to the portion treated with the treating agent of Example11 is colored in red and the remaining portion corresponding to theuntreated portion is colored in black. The copy is clear and distinctwithout mingling of colors.

APPLICATION EXAMPLE 6- Multicolor-forming photosensitive paper for drydevelopment A solution of the following recipe is prepared:

G. 4-diazo-N,N-dimethylaniline chloride 30 Tartaric acid 2O Ethyleneglycol 50 2,4,2,4'-tetrahydroxydiphenyl sulfide 11 Thiourea 25 Zincchloride 50 Patent Blue 0.1 Water Balance Total--1 liter.

14 {copy is obtained usable as the intermediate in which a portioncorresponding to the portion of the original treated with thecomposition of Example 2 is colored in red and another portioncorresponding to the untreated portion of the original is colored inyellowish brown. The intermediate is clear and excellent in colordistinction.

APPLICATION EXAMPLE 7 Multicolor-forming sensitive paper in use foreither dry or wet development A solution of the following recipe isprepared:

Total-l liter.

From the above solution, a photosensitive paper is prepared byconducting the coating and drying in the same manner as in ApplicationExample 1. The so formed photosensitive paper is piled on an original, aportion of the back surface of which is treated with the ink-likecomposition prepared in Example 1 and another portion of the backsurface of which is treated with the treating material prepared inExample 2, in a manner such that the treated surface of the originalconfronts the photosensitive layer of the photosensitive paper. Then theassembly is heated and light-exposed by means of a mercury lamp,followed by development with gaseous ammonia and steam or with analkaline liquid developer of the following recipe:

G. Postassium carbonate 20 Sodium thiosulfate 40 Sodium bicarbonate 30Potassium tetraborate 5 Water Balance Total-1 liter.

Thus a clear three-color reproductive copy without any substantialmingling of colors is obtained, in which a portion corresponding to theportion of the original treated with the composition of Example 1 iscolored in yellow, a portion corresponding to the portion of theoriginal treated with the composition of Example 2 is colored in red andthe remaining portion corresponding to the untreated portion of theoriginal is colored in blue.

APPLICATION EXAMPLE 8 Total-l liter.

The above solution is coated on a base paper of a photosensitive paperby a customary method using an air knife coater or the like and dried.The so formed photosensitive paper is piled on an original, the backsurface of a portion of which is treated with the waxy compositionprepared in Example 8, in a manner such that the photosensitive layer ofthe photosensitive paper confronts the treated surface of the original.Then the assembly is heated and light exposed by means of a mercrurylamp and a liquid developer having the following recipe NW acid 15'Potassium carbonate 80 Sodium bicarbonate 30 Sodium thiosulfate O BoraxWater Balance Tota11 liter.

is applied to the heated and light-exposed photosensitive paper by rollcoating or spraying to develop the photo sensitive paper. Thus atwo-color copy of a clear color distinction is obtained in which theportion corresponding to the portion of the original treated with thecomposition of Example 8 is colored in red and other portion corresponding to the untreated portion of the original is colored in bluishviolet.

APPLICATION EXAMPLE 9 Multicolor-forming film A solution of thefollowing recipe is prepared:

4 diam-2,5 dibutoxy N phenyl morpholine /2ZnCl g Citric acid g 10fl-Hydroxynaphthoic acid ethanol amine g 7 Triacetate resin .g 15 OilBlue g 0.2 Acetone ml 40 Methanol ml 700 The solution is coated on apolyester film by a rod coater and dried at a relatively low temperature(40-50 C.) by warm air to form a photosensitive film. The film is piledon an original in which a part of the back surface of an original imageis treated with the ink-like composition prepared in Example 1 andanother part of the back surface of the original image is treated withthe ink-like composition prepared in Example 2. The assembly is heatedand exposed to light by a mercury lamp. The photosensitive filmcontaining a latent image of the diazonium salt is developed withgasified ammonium and steam. Thus, a clear three-color reproductive copywithout any substantial mingling of colors is obtained, in which aportion corresponding to the part treated with the treating compositionof Example 1 is colored in yellow, a portion corresponding to the parttreated with the treating composition of Example 2 is colored in red,and another portion corresponding to the untreated part of the originalis colored in blue.

What we claim is:

1. A process for multicolor reproduction, which comprises (A) exposingimagewise to actinic light an assembly of (i) an original sheet havingopaque image areas and transparent non-image areas on one surface and alayer of at least one thermovolative or sublimable azo coupler (a)contiguous with pre-selected opaque image areas, said thermovolatile orsublimable azo coupler (a) being a thermovolatile or sublimable acidaddition salt of a thermovolatile or sublimable azo coupling componentcontaining an amino group, selected from the group consisting ofaminophenols, aromatic amines and active methylene group-containingamines, and (ii) a diazo-type photosensitive material having aphotosensitive layer containing at least one photosensitive diazoniumsalt (c), an acidic stabilizer and an azo coupler (b) having asubstantially lower rate of coupling with the diazonium salt (c) underthe developing conditions that that of the azo coupler (a), saidoriginal sheet (i) being superposed on said diazo-type photosensitivematerial (ii) so that the layer of the azo coupler (a) comes intoface-to-face contact with the photosensitive layer; (B) heating saidassembly thereby to heat-transfer said layer of the coupler (a) to thecorresponding position on the surface of said photosensitive layer, saidsteps (A) and (B) being performed simultaneously or in the sequence of(A) to (B) or (B) to (A); and (C) contacting the exposed photosensitivematerial with a mixture of ammonia and steam or an alkali-containingaqueous liquid developer to thereby develop said photosensitivematerial, whereby in the unexposed latent image area of the portion towhich the coupler (a) has been heat-transferred, a dye (c)(a) having acertain hue or color is formed by the selective reaction between theheat-transferred coupler (a) and the diazonium salt (c) and at the sametime, in the unexposed latent image areas to which the coupled (a) hasnot been heat-transferred, a dye (c)-(b) having a different hue or colorfrom said dye (c)-(a) is formed by the reaction of the coupler (b) withthe diazonium salt (c), thus producing a multi-colored copied image.

2. The process of claim 1 wherein said thermovolatile or sublimable azocoupler has a melting point of C.

3. The process of claim 1 wherein said thermovolatile 0r sublimable acidaddition salt is a salt of a thermovolatile or sublimable azo couplingcomponent containing an amino group with an acid selected from the groupconsisting of hydrohalogenic acids, organic sulfonic acids, chloroaceticacid, chloropropionic acid, acetic acid, salicylic acid,2,6dichlorobenzoic acid, 3,4-dimethylbenzoic acid, oxalic acid, oxalicacid hydrate, o-sulfobenzoic acid, trichloroacetic acid, formic acid,methacrylic acid and butyric acid.

4. The process of claim 1 wherein said thermovolatile or sublimable acidaddition salt of a thermovolatile or sublimable azo coupling componentis selected from the group consisting of metaaminophenol hydrochlorideand 1-phenyl-3-methyl-pyrazolone(5) hydrochloride.

5. A process for multicolor reproduction, which comprises (A) exposingimagewise to actinic light an assembly of (i) an original sheet havingopaque image areas and transparent non-image areas on one surface and alayer of at least one thermovolative or sublimable azo coupler (a)contiguous with pre-selected opaque image areas, said thermovolatile orsublimable azo coupler (a) being a thermovolatile or sublimable acidaddition salt of a thermovolatile or sublimable azo coupling componentcontaining an amino group, selected from the group consisting ofaminophenols, aromatic amines and active methylene group-containingamines, and (ii) a diazo-type photosensitive material having aphotosensitive layer containing at least one photosensitive diazoniumsalt (c), said original sheet (i) being superposed on said diazo-typephotosensitive material (ii) so that the layer of the azo coupler (a)comes into face-to-face contact with the photosensitive layer; (B)heating said assembly thereby to heat-transfer said layer of the coupler(a) to the corresponding position on the surface of said photosensitivelayer, said steps (A) and (B) being performed simultaneously or in thesequence of (A) to (B) or (B) to (A); and (C) contacting the exposedphotosenstive material with an alkali-containing aqueous liquiddeveloper containing an azo coupler (b) having a substantially lowerrate of coupling with the diazonium salt (c) under the developingconditions that that of the azo coupler (a), to thereby develop saidphotosensitive material, whereby in the unexposed latent image area ofthe portion to which.

the coupler (a) has been heat-transferred, a dye (c)-(a) having acertain hue or color is formed by the selective reaction between theheat-transferred coupler (a) and the diazonium salt (c) and at the sametime, in the unexposed latent image areas to which the coupler (a) hasnot been heat-transferred, a dye (c)-(b) having a different hue or colorfrom said dye (c)-(a) is formed by the reaction of the coupler (b) withthe diazonium salt (c), thus producing a multicolored copied image.

6. The process of claim 5 wherein said thermovolatile or subsimable azocoupler has a melting point of 100- 150 C.

7. The process of claim 5 wherein said thermovolatile or sublimable acidaddition salt is a salt of a thermovolatile or sublimable azo couplingcomponent containing an amino group with an acid selected from the groupconsisting of hydrohalogenic acids, organic sulfonic acids, chloroaceticacid, chloropropionic acid, actic acid, salicylic acid,2,6-dichlorobenzoic acid, 3,4- dimethylbenzoic acid, oxalic acid, oxalicacid hydrate, osulfobenzoic' acid, trichloroacetic acid, formic acid,methacrylic acid and butyric acid.

8. The process of claim 5 wherein said thermovolatile or sublimable acidaddition salt of a thermovolatile or sublimable azo coupling componentis selected from the group consisting of metaaminophenol hydrochlorideand 1-phenyl-3-methyl-pyrazolone(5) hydrochloride.

References Cited UNITED STATES PATENTS 18 2,531,091 11/1950 Van Dormael9691 R 3,343,960 9/1967 Sus 9691 R 1,966,755 7/1934 DHauterive 9691 R3,427,165 2/ 1969 Champ et a1. 9691 R 3,007,795 11/1961 Haydn et a1 9691R 3,510,336 5/1970 Figor 9649 X 2,789,904 4/1957 Benbrook et a1 96492,747,999 5/1956 Yutzy et a1 9649 2,542,716 2/ 1951 Slifkin 9691 RFOREIGN PATENTS 1,000,151 8/ 1965 Great Britain 9649 OTHER REFERENCESLandau, R. et al., J. of Photo. Sci., vol. 13, May 1965, pp. 144-151.

CHARLES L. BOWERS, JR., Primary Examiner US. Cl. X.R.

